Detergent composition



A. KE SSLER ETAL DETERGENT COMPOSITION July 25, 1967 5 Sheets-Sheet; 1

Filed Dec. 23, 1965 Fig. 1

252 @5502, 9:50 25m 68mm Ratio of Detergent (A) to Detergent (B) I (A) 1* 3 N N d N lk i Deiergem (B) lmethy coconutu y ommen o)- 2-hydroxypropane-l-sulfonute Detergent (A) 11 oetergem (8) -T- Dodecytdlmethyl omme oxide I INVENTORS Phllhp F Pfluumer Adriou'n Kessler ATTORNEYS July 25, 1967 KESSLER ET AL 3,332,875

DETERGENT COMPOS ITION Fig. 2

Percent Suds During Washing (Suds Stability) Detergent (A) with )4 Curbons Detergent (B) Detergent (A) with IS Corbons Detergent (B) it Detergent (A) with 12 Curbons Detergent (B) )K- O 5 IO )5 v Rs 1N ENTO Retro of Detergent (A) to Detergent (B) E Pfloumer Adriuun Kessler *E 3-(N,N-dimethyl-N-coconutolkyl ammonia)- BY 2-hydroxypropune-l-sulfonate l 5 ATTORNEYS July 25, 1967 A E R ET AL 3,332,875

DETERGENT COMPOSITION Filed Dec. 23, 1965 3 Sheets-Sheet 3 Percent Suds During Washing (Suds Stability) 3O 25 2O l 5 IO O O 5 (0 (5 2O 3O Raiio of Demrgen't (A) 10 Deiergent (B) m ABS 3-(N,N-dimethyl-N-coconutalkyl ammonia)2-hydroxypropanel-sulfonoie m Detergent (A) 3(N,NdimeihylN-hexudecylummonio)-propune|-sulfonuie m De iergeni (A) 3(N,N-dimethylN-tul|owolkyl ummonlo)-2-hydroxypropunelsulfonote Deiergenf (A) v Hydroxymethyl undecyl sulfoxide INVENTORS Phillip F. Pflaumer Adrioun Kessler ATTORNEYS United States Patent 3,332,875 DETERGENT COMPOSITION Adriaan Kessler and Phillip Floyd Pflaumer, Cincinnati, Ohio, assignors to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio Filed Dec. 23, 1965, Ser. No. 524,364 18 Claims. (Cl. 252-137) This is a continuation-in-part of application Serial No. 423,008, now abandoned, filed January 4, 1965.

This invention relates to a novel detergent composition. It also relates to a detergent composition which embodies a synergistic mixture of surface active compounds.

The compositions described herein are useful for both light-duty and heavy-duty applications. They have special usefulness, however, in connection with detergent compositions designed for light-duty cleaning situations. The terms light-duty and heavy-duty as applied to detergency have acquired fairly definite meanings in the art.

The term light-duty is used in the description of this invention in its usually accepted context, i.e., namely, as a semispecialty product designed for dish-washing and laundering fine fabrics by hand. The term is also used to differentiate between this class of products and the heavy-duty laundering products used in standard and automatic washing machines which depend substantially for their satisfactory performance on the use of large amounts of various types: of additives such as suds boosters, detergency builders, sequestering agents and other similar functional ingredients.

Light-duty applications include the hand washing of dishes and lightly soiled fine fabrics which fabrics cannot as a rule withstand the vigorous treatment of machine laundering. Also, light-duty washing situations are those which generally call for a gentle washing action in cool or lukewarm water. It is well known by those skilled in the art that compositions designed for such uses must have certain performance properties which distinguish them from heavy-duty cleaning compositions. For instance, they must be mild to the skin, possess high sudsing properties, and also possess cleaning power in water solutions having cool or lukewarm temperatures, e.g. below 100 F.

On the other hand, heavy-duty applications are those cleaning situations which involve heavily soiled fabrics and clothing. One of the considerations involved in such cleaning processes is the use of vigorous mechanical action usually in hot water having temperatures between about 120 F. and up to about 200 F. The problems presented by high soil loads on fabrics such as cotton are unlike those dealt with in light-duty situations. Thus the different cleaning situations require the use of specially formulated detergent compositions.

In addition to the desirable properties mentioned above in connection with light duty uses, a deter-gent composition should serve as a Wetting agent to solubilize and emulsify greasy soils and help remove them from soiled articles, especially from dishes. The composition should be able to disperse and suspend soil once it is removed.

from the articles being washed so that the soil does not redeposit on the articles. A light-duty dishwashing composition moreover, should be able to provide quickly a copious amount of stable suds that will form a long lasting suds layer over the washing solution. The blanket of suds produced should be so stable that it will last throughout the entire washing operation. The cleaning capability of a dishwashing solution is frequently gauged by the amount of suds present during the washing process. In. addition, the detergent composition should perform these functions efliciently over the wide range of "ice washing conditions normally encountered in dishwashing and fine fabric laundering processes (water temperature, water hardness, soil type, soil load, etc.). Special caution must be taken to insure that a dishwashing composition will be mild on the skin. Still further, it is desirable that a detergent composition when formulated into a liquid product should provide a physically stable system over a wide range of storage conditions. Economic considerations also play an important role in the preparation of these types of compositions.

It is a primary object of the present invention to provide a detergent composition preferably a liquid formulation which performs satisfactorily in all or most of the foregoing areas, and which excels in some of them, especially sudsing. Thus, it is an object of this invention to provide a liquid detergent composition which offers synergistic sudsing performance characteristics which make it especially valuable for dishwashing and fine fabric laundering. It is another object to provide a. light-duty liquid composition which consists essentially of an aqueous vehicle and a synergistic mixture of the hereinafter described active detergent compounds. These and other objects of the present invention will become apparent from the following description.

FIGURES l and 2 are graphs presenting data showing the surprising synergistic sudsing results made possible by the detergent compositions of the present invention. FIGURE 3 presents data for comparison purposes.

All percentages and ratios given hereinafter are by weight unless otherwise specified.

It has now been discovered that a detergent composition having superior sudsing performance characteristics can be prepared which consists essentially of a synergistic mixture of Detergent A and Detergent B wherein Detergent A is an ingredient which comprises from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C, wherein:

(a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene l-sulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including by weight about 10% to about 25% of an alphabeta unsaturated isomer, about 30% to about 70% of a beta-gamma unsaturated isomer, about 5% to about 25% of a gamma-delta unsaturated isomer, and about 5% to about 10% of a delta-epsilon unsaturated isomer;

(b)-said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sul-' fonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom; and p (c) said Component C is a mixture comprising from 30- water-soluble salts of alkene disulfonates containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached 3 to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group; and wherein Detergent B is a compound selected from the group consisting of (1) Zwitterionic quaternary ammonium compounds having the formula:

wherein R is an alkyl radical containing from 12 to 14 carbon atoms,

R and R each are members selected from the group consisting of methyl, ethyl and hydroxyethyl,

R is an alkylene radical having from 1 to 3 carbon atoms, and

B is a member selected from the group consisting of hydrogen and hydroxyl;

[2) a tertiary amine oxide detergent compound having the formula RR"R"'N O, and

[3) a tertiary phosphine oxide detergent compound hav ing the formula R'R"R'P+O, wherein in both (2) and (3) R is an alkyl or monohydroxyalkyl radical containing from about 12 to 14 carbon atoms,

i and R' are each members selected from the group consisting of methyl, ethyl and hydroxyethyl.

According to the present invention the synergistic :udsing results are obtained when Detergent A and Deergent B are present in admixture at a ratio of Detergent A to Detergent B of from about 5:1 to about 1:5, 9y weight. Outstanding results are obtained within a narrower preferred ratio of Detergent A to Detergent B )f 3:1 to 1:3, by weight.

According to the present invention, Detergent A is itelf a mixture of certain compounds. As noted above it s basically a mixture of three components each of which las a specific composition. A detailed discussion of the nakeup of Detergent A is presented below.

A preferred percentage range by weight for Com- )onent A is from about 35% to about 65%, for Comronent B it is from about 25% to about 60%, and for Iomponent C it is from about 3% to about 12%. Comlonent A is comprised essentially of the prescribed anges of the following compounds.

In the preceding formulas x is an integer in the range rom about 6 to about 10, preferably about 8 to 10, nd M represents any cation that forms a water-soluble alt such as alkali metals, e.g. sodium and potassium, nd ammonium, and substituted ammonium compounds, .g. trialkylammonium and trialkylolammonium comounds. Specific examples of substituted ammonium ompounds are triethylammonium, trimethylammonium, nd triethanolammonium. Others will be apparent to rose skilled in the art. The symbol x and M have the me meaning throughout the description of the present lvention. There can also be present, minor amounts of ther double-bond positional isomers. This is the case, )r example, when the composition is prepared by the xlfonation of alpha olefins with uncomplexed sulfur 4 trioxide. Such minor amounts, i.e. less than 10% by weight, do not materially alter the excellent detergent properties of the composition.

Whereas, Component A is a blend or mixture of certain unsaturated isomeric aliphatic compounds, Component B consists of a mixture of certain saturated aliphatic compounds. A minor amount of unsaturation can be included in this mixture but preponderantly the compound are saturated. The bifunctionality of these alkane compounds is due to the presence of a hydroxyl group and a sulfonate radical on the same molecule. It has been discovered that the sulfonate radical must be located on the terminal carbon atom. It also has been discovered that the situs of the hydroxyl group is an especially important factor in the compounds that can comprise -Component B. For example, if the hydroxyl group and the sulfonate radical are attached to adjacent carbon atoms, the valuable detergent properties of the Componeut B compounds are substantially decreased. This is especially true when the alpha and beta carbons are the two sites of attachment. The critical structural arrangement which must exist in order for the compounds to be detergents, is that the sulfonate radical must be in the alpha position and the hydroxyl radical must be attached to a carbon atom at least two carbons removed, for example, to the third, fourth or fifth carbons, i.e. on the gamma, delta, or epsilon carbons. In other words, the carbon to which the hydroxyl group is attached should be separated from the carbon bearing the sulfonate radical by at least one methylene group along the aliphatic chain.

Thus, Component B consists of a mixture of the following bifunctionally-substituted saturated aliphatic compounds.

Permis- Preferred sible Range, Range, percent percent OHE(OHZ)X CH2OH2OH(OH)GHZCHESOBM- 10-90 25-75 CHa(OH2)XOHzCH(OH) CHzCHzCHzS 03M. 10-90 25-75 OH3(CH);CH(OH)OHzOH2OHzCH2SOaM 10-90 25-75 The value of x and M are as previously set forth.

Component B can also include minor quantities, for example, less than about 10% of compounds wherein the hydroxyl group is attached elsewhere along the carbon chain, e.g. on the sixth carbon atom, without materially altering the overall detergent properties of the compositions. However, at least 90% of the hydroxyl radical substitutions must be in the 3, 4, and 5 positions. The 3-, 4-, and S-hydroxy n-alkyl sulfonate compounds, illustrated above, are preferred ingredients in Component B.

In this same connection, it has also been noted that corresponding beta-hydroxy n-alkyl sulfonate compounds are relatively poor detergent compounds. Not only are they comparatively poor detergents, but it has been discovered also that such compounds constitute an actual load on the present detergency system. For this reason, the level of such compounds should be held to a minimum. It is noted though, that minor amounts of betahydroxy n-alkyl sulfonate compounds can be tolerated in the synergistic compositions of this invention provided that components A, B, and C of Detergent A otherwise contain the essential ingredients herein described in the proportions and percentages specified.

The alkene disulfonates should preferably comprise from about 40% to about of the highly polar polyfuncti-onally substituted aliphatic compounds which make up Component C. These alkene disulfonates should preferably contain from about 12 to about 16 carbon atoms. As mentioned above, one sulfonate group is attached to the terminal carbon atom. The second sulfonate group is attached to an internal carbon atom that is not more than about six carbon atoms removed from the terminal car-- bon. In other words, the second sulfonate functional group can be attached to the second through about the seventh carbon atom. Component C can also include minor amounts of compounds in which the second sulfonate is located more internally than the seventh carbon, such as, for example, on the eighth carbon, etc. There is no apparent advantage in having these latter compounds present in the composition, however. According to a preferred embodiment, the major portion, that is from about 60% to about 95% of the alkene disulfonates, should be 1,2 and 1,3 disulfonates.

The alkene double bond can be distributed between the terminal carbon and about the seventh carbon atom; such unsaturation includes, for instance, alpha-beta, betagamma, gamma-delta, delta epsilon, epsilon-zeta, and zetaeta unsaturation. Preferably, the double bond should be distributed between the second to the sixth carbon atom. It should be noted that the allcene double bond can be even more internally located than between the zeta-eta carbons, but again no apparent advantage is gained thereby.

Thus, it can be seen that the alkene disulfonates of Component C contain the polyfunctional combination of a double bond and two sulfonate groups in an important structural relationship. The preferred compounds as ingredients of the alkene disulfonate portion of Component C are 2-alkene-1,2-disulfonate; 3-alkene-1,2-disulfonate; and 4-alkene-1,2-disulf-onate of the 1,2 disulfonate species; and 3-alkene-1,3 disulfonate; 4-alkene-1,3-disulfomate; and -alkene-1,3-disulfonate of the 1,3 disulfonate species. The alkene group can contain from about 12 to about 16 carbon atoms and preferably about 14 to 16 carbon atoms. The sodium and potassium salts of these compounds are preferred.

Examples of alkene disulfonate compounds are the following in which a carbon chain length of 16 was selected as being representative, having sulfonate attachment sites of 1,2 and 1,3;

As mentioned above, Component C contains the aforementioned and illustrated alkene disul-fonates. It also contains from about 5% to about 70%, and preferably about 20% to about 60%, water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms. The terminal carbon atom has attached to it one of the sulfonate groupsrThe second sulfonate group can be attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon'atom. The required hydroxy group is attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group.

The preferred sites of attachment for the hydroxy group on the 1,2 disulfonate species are the fourth and fifth carbon atoms to yield 4-hydroxyalkane-1,2-disulfonates and S-hydroxyalkane-1,2-disulfonates. For the 1,3-disulfo nates the preferred sites of attachment for the hydroxy group are the fifth and sixth carbon atoms to yield 5- hydroxyalkane-1,3-disulfonates and 6-hydroxyalkane-l,3- disulfonates. The alkane hydrocarbons as before are those having 12 to 16 carbon atoms and preferably about 14 to 16 carbon atoms. According to a preferred embodiment, the major portion, that is, from about 60% to about of the hydroxy disulfonates should be 1,2 and 1,3- disulfonates.

Thus, for example, the following compounds are contemplated. Again, a 1-6 carbon 1,2 and 1,3 disulfonate compound is presented as being representative.

It is postulated that a second polar group, as in Components B and C, spaced a critical distance from a te r minally attached polar group in a detergent molecule modifies the crystalline latice structure in such a way as to improve markedly the solubility characteristics of the compound. While this is not known for certain, it is offered as one possible explanation for the exceptional detergent properties of the compositions of the present invention.

Detergent A as described herein can be prepared in any suitable manner so long as the above teachings are adhered to. For instance, each of the ingredients can be synthesized separately and then mixed according to the stated proportions. On the other hand, it is possible to prepare Detergent A of the present invention according to a novel process described in copending patent application Serial No. 423,292, filed January 4, 1965 by Adriaan Kessler and Phillip F. Pflaumer.

If it is desired to synthesize separately the individual components of Detergent A, it is possible to do so according to the procedures in the following discussion. Any other suitable methods can be used. The symbol R as used in the following equation represents an aliphatic hydrocarbon radical that would allow for a total of carbon atoms in the molecule between about 12 and about 16. The alpha-beta unsaturated sulfonate containing aliphatic compounds of Component A can be prepared readily by dehydrochlorinating a Z-chlorosulfonic acid derivative. A fairly detailed discussion of a suitable preparative route appears in an article in the Journal of The Chemical Society, 1949, page 46, written by I. D. Rose and A. Lambert. The starting step for this synthesis is a reaction be tween a long chain epoxide and sodium bisulfite to produce a Z-hydroxy-l-sulfonate derivative of the particular long chain epoxide used. This reaction product is condensed with PCl to prepare the aforementioned 2-chlorosulfonic acid derivative which in turn is reacted with sodium carbonate to yield an alpha-beta unsaturated compound.

The other preferred double-bond positional isomers of Component A, i.e., the beta-gamma, gamma-delta, and delta-epsilon can be prepared by the thermal dehydration of hydroxy-sulfonates. According to the following reaction, the thermal dehydration of the sodium salt of 3- hydroxy-sulfonate results in the preparation of a reaction mixture containing the beta-gamma isomer and the gamma-delta isomer.

2O ROHzGH (OH) O H H23 OaNa Similarly a reaction mixture of a gamma-delta and a delta-epsilon double-bond isomer compound can be prepared by using a 4-hydroxysulfonate as a starting material:

The foregoing synthesis of the double-bond positional isomers follows closely the well known dehydration of an organic alcohol as is mentioned in such standard texts as Whitmores Organic Chemistry, second edition, pages 39-41.

There is no need to separate the reaction product of the two illustrated dehydration reaction. The reaction product can be formulated directly into a detergent composition according to the present invention. If, for some reason, it is desired to work with pure ingredients, they can be separated into pure forms.

The hydroxy sulfonates of Component B, such as the preferred 3-, 4-, and S-hydroxy compounds can be prepared by the free radical addition of sodium bisulfite to ;he corresponding 3-, 4-, or S-hydroxy-l-olefin, respectively:

Free Radical atalyst RCH(OH)CH=CH1 NaHSO;

aldehyde Grignard 3-hydroxy-Lolefin Reagent aldehyde G1 ignard Reagent A discussion of the conversion of hydroxyolefins proluced by preceding equations (a) and (b) to hydroxy 1ulfonates appears in an article Written by J. Willens, Buletin of the Chemical Society of Belgium, vol. 64, page 127 (1955 It is to be understood that other hydroxy sulfonates as desired can be prepared by using different Grignard reagents in the reaction equation set forth above.

The alkene disulfonates and the hydroxy disulfonates which comprise Component C may also be prepared sep- 5 arately by any known manner. For instance, the hydroxy disulfonates may be prepared by epoxidizing olefin sulfonic acid isomers, and then opening the epoxide ring with sodium bisulfite by standard reaction techniques. The hydroxy disulfonates may then be dehydrated by reactions known to those skilled in the art to yield the corresponding isomeric alkene disulfonates.

As mentioned earlier, the Detergent A components should contain from about 12 to about 16 carbon atoms. It is preferred, however, to have the compounds contain from 14 to 16 carbon atoms. It is not necessary that each of the compounds contain the same number of carbon atoms. Mixtures of different chain lengths within the prescribed ranges can be used.

The following compositions are illustrative of the make up of Detergent A according to the present invention wherein the percentages are by weight and wherein Components A, B and C total up to 100% of Detergent A. The percentages listed for each ingredient are by weight of that particular ingredient in Detergent A.

Detergent A can be comprised as follows with a chain length of 16 carbons being representative:

Component A: Percent C14H29CH=CHSO3N21 C H CH=CHCH SO Na 33 C H CH=CH CH SO Na C H CH=CHCH CH CH SO Na 6 Total Component A 6;

35 Component B: Percent C H CH(OH)CH CH SO Na C12H25CH CH2CH2CH2SO3NE1 5 Total Component B 25 Component C: Percent C H CH=C(SO Na)CH SO Na This Detergent A composition listed above has excellent detergent and synergistic sudsing properties when mixed with Detergent B according to the proportions described herein.

1 Another illustrative example of Detergent A is as folows:

Component A: Percent 7 O C H CH=CHSO Na 9 C H CH=CHCH SO Na c gHgscH cHcHzcHgsogNa. C H CH=CHCH CH CH SO Na Total Component A 65 9 Component B: Percent C13H27CH CH CH SO Na C H CH(OH)CH CH CH SO Na 10 C H CH(OH)CH CH CH CH S Na 3 Total Component B 23 Component C: Percent CH (SO Na) CmH a) -CH SO Na Na )-CH2 -CH SO Na C mH21-CH CH CHzcH (SO Na CH=CHSO Na C H -CH -CHgCH3-C SO Na CH2S03Na (SO Na)CH SO Na 3.0 C H CH CH(OH)--CH -CH -CH (SO Na)-CH SO Na 1.0

--CH -CH SO Na 0 25 Total ComponentC 12 This Detergent A composition also offers excellent detergent properties of cleaning and synergistic sudsing in admixture with Detergent B as described herein.

The following is a list of the zwitterionic quaternary ammonium compounds which can be used in admixture with Detergent A, described above, to obtain the beneficial sudsing synergism which forms the basis of the present invention:

3-(N,N-dimethyl-N-dodecylammonio)-2-hydroxypropanel-sulfonate 3-(N,N-diethyl-N-dodecylammonio)-2-hydroxypropanel-sulfonate 3-[N,N-di(hyd-roxyethyl)-N-dodecylammonio]-2-hydroxypropane-l-sulfonate 3-(N,N-dimethyl-N-tetradecylammonio)-2-hydroxypropane-1-sulfonate 3 N,N-diethyl-N-tetradecylammonio -2-hydroxypropanel-sulfonate 3 [N,N-di (hydroxyethyl) -N-tetradecylammonio] -2- hydroxypropane-l-sulfonate 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-lsulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 3-(N,N-diethyl-N-alkylammonio)-2-hydroxypropane-1- sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 3-[N,N-di(hydroxyethyl)-N-alkylamrnonio]-2-hydroxypropane-1-sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol 3-(N,N-dimethyl-N-dodecylammonio)-propane-1- sulfonate 3 (N,N-diethyl-N-dodecylammonio -propane-1-sulfonate 3 (N,N-dimethyl-N-tetradecylammonio -propane-1- sulfonate 3 N,N-dimethyl-N-alkylammonio -prop anel-sulfonate,

the alkyl group being derived from the middle-cut of coconut fatty alcohol 4- (N,N-diethyl-N-alkylammonio -2-hydroxybutane-1- sulfonate, the alkyl group being derived from the mid-, dle-cut of coconut fatty alcohol 2- [N,N-di (hydroxyethyl) -N-alkylamrnonio] -ethane-1- sulfonate, the alkyl group being derived from the middle-cut of coconut fatty alcohol.

As noted above in the examples of suitable zwitterionic quaternary ammonio compounds, the long chain aliphatic radical can be a C (dodecyl) or C (tetradecyl) radical or alternatively can be derived from a natural source such as the middle-cut of distilled coconut fatty alcohol which consists of a mixture of various chain lengths being approximately 2% C 66% C 23% C and 9% C Thus, a preponderant chain length C and C has been found essential. It is to be understood, however, that minor amounts ofingredients Whose chain length is less than 10 and greater than 14 can be tolerated without upsetting the desirable properties of the composition. The coconut alkyl species of the zwitterionic quaternary ammonium compounds described above are the preferred compounds of this type according to the present invention.

The quaternary ammounium compounds which are useful in terms of the present invention can be prepared by any known method, and the way in which these compounds are prepared forms no part of the present invention. One acceptable synthesis route which is described in detail in German Patent 1,018,421, comprises reacting an aliphatic tertiary amine such as N-dodecyl-N,N-dimethyl amine with a propane sulfone.

A corresponding hydroxy compound such as 3-(N,N- dimethyl-N-dodecylammonio)-2-hydroxypropane 1 sulfonate can be prepared readily by reacting glycerol-monochlorohydrin sulfonic acid with a suitable tertiary amine such as dodecyl dimethyl amine. This process is described in German Patent 651,733. Use of a coconut alkyl dimethyl amine or tetradecyl dimethyl amine will result in the corresponding desired quaternary compounds.

The tertiary amine oxide detergent compounds which can be used according to the present invention as Detergent B have the general formula set forth above,

RIRIIRIIINQO In this formula the arrow is a conventional representation of a semipolar bond. They can be prepared by any known manner, for example by the direct oxidation of an appropriate tertiary amine. It will be noted that the amine oxides used in the present invention contain a high molecular Weight alkyl chain, R in the formula, containing from about 12 to about 14 atoms. The alkyl group can be dodecyl, tetradecyl, or mixtures thereof, as are derived for example from natural sources. A convenient natural source of preponderantly C and C chain lengths is the middle-cut of coconut fatty alcohol which has the approximate chain length composition: 2% C 66% C 23% C and 9% C The middle-cut of coconut fatty alcohol is a good illustration that while the C -C must be present in preponderant amounts, the novel composition can tolerate minor amount of other chain lengths such as C and C The preferred tertiary amine oxides within the full breadth and scope of this invention are dodecyldimethyl amine oxide, alkyldimethyl amine oxide (where the alkyl group is the middle-cut of coconut fatty alcohol) and tetradecyldimethyl amine oxide.

Examples of suitable amine oxide detergent compounds are listed below:

The tertiary phosphine oxides of the present invention have the formula R'R"R"P- O wherein the substituents have the same meaning as for the amine oxides. The

chemistry of the molecule requires that R be much larger than R and R' in order for the compound to have detergent properties. Moreover, it has been discovered that the synergistic sudsing behavior occurs when the high molecular Weight alkyl group R contains from about 12 to about 14 carbon atoms and the lower alkyl radicals are selected from methyl, ethyl and hydroxyethyl. De-

sirable surface active properties for the purpose of the present invention are lost if these limitations are not followed when the compounds are mixed with Detergent A, described above.

As mentioned previously, the tertiary phosphine oxides of this invenion can be prepared by methods known in the prior art. A good method is discussed, for example, in French Patent 1,317.586.

Examples of suitable teritary phosphine oxides are listed below:

Dodecyl dimethyl phosphine oxide Tetradecyl dimethyl phosphine oxide Dodecyl diethyl phosphine oxide Tetradecyl diethyl phosphine oxide Beta hydroxy dodecyl di(hydroxyrnethyl) phosphine oxide Tetradecyl di(hydrxymethyl) phosphine oxide Dodecyl di(hydroxyethyl) phosphine oxide Tetradecyl di(hydroxyetl1yl) phosphine oxide.

Dodecyl dirnethyl phosphine oxide, alkyldimethyl phosphine oxide (wherein the alkyl group is derived from the middle-cut of coconut fatty alcohol), and tetradecyl dimethyl phosphine oxide are the preferred tertiary phosphine oxides in accordance with the present invention.

Tertiary amine oxides and phosphine oxides are known as abroad class of compounds. What has not been known prior to the present invention was that certain specific members of such classes of compounds when combined with Detergent A described above, provide synergistic sudsing performance. It is significant that not all amine oxides or phosphine oxides give these excellent results since only those described above are operable within the scope of the present invention.

The synergistically improved sudsing performance of the novel compositions of the present invention was dis covered by preparing light-duty liquid compositions containing different detergent compounds as sole cleaning agents and also representative mixtures of such detergent compounds. The compositions were standardized to include a total of 30% by weight of an active detergent ingredient with the balance, 70%, being an aqueous vehicle.

Detergent A and Detergent B were each first tested separately and then in certain prescribed mixtures. Thus, for example, a composition was prepared consisting of 30% of just Detergent A and 70% water. Another composition was prepared consisting of 30% of just Detergent B and 70% water. Then mixed compositions were prepared consisting of 25% Detergent A and 5% Detergent B, 20% Detergent A and Detergent B, Detergent A and 15% Detergent B, 10% Detergent A and Detergent B, 5% Detergent A and Detergent B,

The specific testing procedure designed to evaluate these several detergent compositions under simulated home performance situations is described. A dishpan was prepared containing one gallon of water with a hardness of 7 grains, a temperature of 115 F. and a pH of 7. To this was added 7.25 cc. of each of the detergent compositions being tested. The washing solution containing the detergent composition was mechanically agitated to produce the maximum suds level which was measured. This is referred to as the original suds level. Agitation was by means of a mechanical stirrer.

After this original suds level was obtained, a series of five ordinary dinner plates each soiled with about 2 grams of standardized fatty soil (a triglyceride shortening) were washed in the prepared test solution. The suds height was again measured. This procedure was repeated 21 fixed number of times with a suds height measurement being taken after each set of five dishes were washed. An average was then calculated for the several suds height measurements, and the average was then expressed in terms of a percentage of the original suds height. This percentage figure is regarded as a relative measure of two extremely important areas of dishwashing and fine laundry performance, namely, initial suds volume and even more importantly, suds stability in the presence of increasing soil load. The results are highly dependable and reproducible. Those skilled in performing this evaluation know from experience that a difference in suds height of from about 3% to about 5% is considered significant.

The results of these evaluations are presented in FIG- URES l, 2 and 3 which are described below.

In FIGURE 1, graph line I represents performance data obtained from mixtures of Detergent A and 3-(alkyldimethylammonio)-2-hydroxypropane-l sulfonate where the alkyl group was derived from the middle-cut of coconut fatty alcohol. Graph line II represents performance data obtained from mixtures of Detergent A and dimethyldodecylarnine oxide. In both I and II of FIGURE 1, Detergent A had the following composition; percentages are by weight. The composition was representative of Detergent A compounds which are encompassed within the scope of the present invention.

C11H23CH CH CH SO Na C H CH(OH)CH CH CH SO Na 5 Total Component B 25 Component C: Percent 1.5 C H CH-( OH) CH CH SO Na) CH (SO Na) 3.0 C H CH (OH) CH CH (S0 Na CH CH SO Na) Total Component C 10 The improved synergistic sudsing results were totally unexpected and most surprising was the magnitude of such results. It will be observed from graph line I, in FIGURE 1, that with a Detergent A 3-(N,N-dimethyl-N- coconutalkylammonio) 2 hydroxypropane l sulfonate mixture, it is possible to get sudsing results far superior to either detergent alone, e.g., as much as a 9% improvement over Detergent A alone and up to about 20% suds height improvement over Detergent B, using a ratio of from about 5 :1 to about 1:5 and especially with a ratio of Detergent A to Detergent B of from about 1:1 to about 1:2. It was stated earlier that a difference of from about 3% to about 5% is a magnitude that readily can be discerned in a household situation making the improved performance results depicted by graph line I extremely valuable. An equally impressive improvement was noted with a Detergent A/dodecyl dimethylamine oxide mixture within a ratio range of about 5:1 to about 1:5. The most notable suds height improvement for this latter combination of detergents was found at a ratio of 1:1 and was on the order of about 10% to 11% improvement.

Synergistic sudsing results werealso obtained when 3-(N,N dimethyl N coconutalkylammonio) propane 1 sulfonate and dodecyldimethyl-phosphine oxide were substituted for the Detergent B compounds discussed in accordance with FIGURE 1. The results paralleled very closely the graph lines of FIGURE 1 with the preferred range being between about 3:1 to 1:3. Sudsing synergism can also be obtained by replacing the 3-(N,N-

13 dimethyl-N-coconutalkylammonio) 2 hydroxypropanel-sulfonate represented in graph line I of FIGURE 1, with 3-(N,N-dimethyl-N-tetradecylammonio) 2 hydroxypropane-l-sulfonate, 3-(N,N dimethyl N dodecylammonio)-2-hydroxypropane-1 sulfonate, 3-(N,N- dimethyl-N-dodecylammonio)-propane 1 sulfonate, and 3-(N,N-dimethyl-N tetradecylammonio) propanel-sulfonate. Excellent results are obtained when the tertiary amine oxide of II in FIGURE 1 is replaced by coconutalkyl dimethyl phosphine oxide, tetradecyl dimethyl phosphine oxide, dodecyldimethyl phosphine oxide, coconutalkyl dimethyl amine oxide or tetradecyldimethyl amine oxide. Such compositions are especially useful for dishwashing and fine fabric laundering.

FIGURE 2 illustrates another advantage of the present invention which is that it is possible to prepare a lightduty liquid detergent composition that will provide an excellent degree of suds stability which can be somewhat tailormade so far as speed of sudsing and amount of suds are concerned. This factor is, in part, tied in with the discovery that the length of the long chain hydrophobic group of Detergent A, which can contain from 12 to 16 carbon atoms has an effect upon the synergistic sudsing activity of mixtures of Detergent A with the specific zwitterionic quaternary ammonium compounds, the tertiary amine oxides and the tertiary phosphine oxides of the present invention. It will be appreciated that a person skilled in the art can be guided by the performance results presented in FIGURE 2 and be able to prepare light-duty detergent compositions having different desired levels of sudsing. Such compositions, of course, are intended to come within the scope of the present invention. FIGURE 2 illustrates, among other things, that a composition containing a Detergent A ingredient which has the same composition as in FIGURE 1 (see above), surpassed in performance a Detergent A prepared from sixteen carbon compounds (IV) and a Detergent A prepared from twelve carbon compounds (V), when each was used in combination with 3-(N,N-dimethyl-N-coconutalkylammonio -2-hydroxypropane-l-sulfonate.

The Detergent A represented in FIGURE 2, graph line IV had the following composition wherein each ingredient contained 16 carbon atoms.

(SO Na) 1.0

Total Component C The Detergent A represented in FIGURE 2, graph line V, had the following composition wherein each ingredient contained 12 carbon atoms.

Component A: Percent C H CH=CHSO Na l3 C H CH=CHCH SO Na 33 C H CH=CHCH CH SO Na l3 C H CH=CHCH CH CH SO Na 6 Total Component A 65 14 Component B: Percent C H CH(OH)CH CH SO Na 20 C H CH(-OH)CH CH CH SO Na 5 Total Component B 25 Component C: Percent C H CH(OH)CH CH(SO Na)CH CH (SO Na) 1.0

Total Component C 10 It perhaps should be pointed out that the testing procedure used to obtain the data presented in the figures is dependent to a considerable extent upon the individuals running the tests. Thus, the graphed performance results are most creditable when comparisons are made between various ratios of the detergent actives within a single system and not between different active system. Within any given single detergency system the results are highly reliable and reproducible.

In FIGURE 2the effect of chain length is the principal feature of the present invention which is demonstrated. Tests were only run up to 1:1 ratios. The effect attributed to the chain length of Detergent A is not peculiar to an admixture with 3-(N,N-dimethyl N coconutalkylammonio)-2-hydroxypropane-l-sulfonate which was used as Detergent B in FIGURE 2. The effect is observed according to the present invention, with each of the Detergent B compounds mentioned herein. Based on the results in FIGURE 2 as well as other examples, the 14 carbon chain length for Detergent A represents a preferred embodiment of the present invention.

FIGURE 3 presents sudsing results obtained with mix- .tures of detergent compounds which are different but which are structurally similar to those of the present invention. The data in FIGURE 3 is highly significant because it demonstrates and underscores the fact that the unique synergistic behavior of the compositions of the present invention are not obtained with other compounds which due to their structural similarity might be expected to perform as well as the composition of the present invention.

More specifically, it will be noted that the graph line VI in FIGURE 3 represents an evaluation of a mixture of sodium dodecyl benzene sulfonate, ABS (where the dodecyl radical is straight aliphatic chain) and 3-(N,N- dimethyl-N-coconutalkylammonio) 2 hydroxypropanel-sulfonate zwit-terionic compound. This is the same zwitterionic quaternary ammonium compound which as seen from FIGURES 1 and 2, performed synergistically with Detergent A. From FIGURE 3, it will be seen, that rather than enchancing, it behaves as a load on the sudsing performance of the dodecyl benzene sulfonate species in an unbuilt detergency system. The mixture of 3 (N,N dimethyl N coconutalkylammonio) 2 hydroxypropane-l-sulfonate and straight chain dodecyl benzene sulfonate offer results which are inferior to those obtained by either detergent alone. Whereas dodecyl benzene sulfonate alone, scored 29% and the zwitterionic quaternary ammonium compound scored 23%, a mixture of these two compounds consisting of 25% of the dodecyl benzene sulfonate and 5% of the zwitterionic quaternary ammonium compounds scored only 20%. Measurements for a 20:10 ratio and 15:15 ratio could not be obtained because there was not enough suds to be measured.

Curve VII in FIGURE 3, represents the performance results of a mixture of Detergent A and a zwitterionic quaternary ammonium compound which is a close homolog of those tested above, namely, 3-(N,N-dimethyl-N- hexadecyl-ammonio)-propane-1-sulfonate. The poorer sudsing results are readily apparent at a proportion of 25% to 5%. Complete series of ratios were not run when the clear indication to those skilled in the art was that synergistic results Were not to be obtained. It is noteworthy, that even poorer results were obtained with a composition containing a mixture of Detergent A and 3-(N,N-dimethyl-N-alkylammonio)-2-hydroxypropane-1- sulfonate, where the alkyl group is derived from tallow alcohol, as evidenced by curve VIII. Tallow alkyl is predominantly comprised of C and C chain lengths.

Moreover, curve IX an elevation of a mixture of Detergent A and a sulfoxide compound, hydroxy methyl undecyl sulfoxide, offers another instance for vivid comparison. While sulfoxides are not clearly analagous to phosphine oxides or amine oxides, either structurally or chemically, it is known that such sulfoxides are fairly good sudsing agents, and it might have been expected that the sulfoxides might approach the performance results of phosphine oxides and amine oxides. As graph line IX shows, this was not the case. No synergism was observed. As a sulfoxide compound was substituted at increments of 5% for Detergent A, there occurred only a linear improvement in sudsing, which reached its highest point when the sulfoxide was 100% of the total detergent active.

According to the present invention, the synergistic detergent mixtures of the present invention consisting of the critically proportioned ingredients can be prepared readily into liquid detergent compositions. The essential ingredients for such compositions are the novel synergistic mixture and a liquid vehicle therefor. When used in such a manner the detergent composition can consist of from about 5% to about 50% of the detergent mixture and the balance of 50%95% being water. Preferably, however, the detergent synergistic mixtures can range from about to about 35% by weight of the composition with the remaining 65%90% being water.

Moreover, the detergent mixtures of the present invention can be used with other materials to form complete detergent formulations. Such complete compositions can contain the detergent mixtures of this invention in admixture, for example, with water soluble inorganic alkaline builder salts, organic sequestering agents, or mixtures thereof, hydrotropes, solubilizing agents, antitarnishing agents and water.

The builders and sequestrants can be employed at levels of from about 4% to about 30% by weight of the composition and preferably from about 8% to 25 Water soluble inorganic alkaline builder salts which can be used alone or in admixture are alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium, tripolyphosphate, sodium and potassium carbonate, sodium and potassium tetraborate, sodium and potassium pyrophosphate, sodium bicarbonate, sodium hexametaphosphate, sodium sesquicarbonate, sodium mono and diortho phosphate and potassium bicarbonate. Such inorganic builder salts enhance the overall cleaning characteristic of the novel synergistic mixtures of the present invention. Generally the potassium salts of these compounds are preferred for reasons of solubility. Potassium pyrophosphate is the single preferred builder for use in the present invention.

Examples of organic alkaline builder salts which can be used alone or in admixture are alkali metal, ammonium or substituted ammonium, aminopolycarboxylates, e.g., sodium and potassium N-(2-hydroxyethyl)- ethylenediaminetriacetates, sodium and potassium nitrilotriacetates and sodium, potassium and triethanolammonium N (2 hydroxyethyl)-nitrilodiacetates. Mixed salts of these polycarboxylates are also suitable. Other valuable polycarboxylate builder compounds are the sodium and potassium salts of polymaleate, polyitaconate, and polyacrylate'. The alkali metal salts of phytic acid, e.g., sodium phytate, are also suitable as organic alkaline builder salts (see US. Patent 2,739,942).

Polyphosphonates are also valuable builders in terms of the present invention including specifically sodium and potassium salts of ethane-l-hydroxy-l,l-diphosphonate, sodium and potassium salts of methylene diphosphonate, sodium and potassium salts of ethylene diphosphonate, and sodium and potassium salts of ethane-1,1,2- triphosphonate. Other examples include the alkali metal salts of ethane-2-carboxy-1,l-diphosphonic acid, hydroxymethanediphosphonic acid, carbonyldiphosphonic acid, ethane-l-hydroxy-l,1,2-triphosphonic acid, ethane- 2-hydroxy-1,1,2-triphosphonic acid, propan:e-1,1,3,3-tetraphosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and propane-1,2,2,3-tetraphosphonic acid.

Hydrotropes can be added if desired to increase the compatibility of the ingredients of the formulations of this invention. Preferred hydrotrope anions are benzene sulfonate, sylene sulfonate, and toluene sulfonate. They are preferably used as their soluble salts such as: ethanolammonium, diethanolammonium, and triethanolammoniu m, and especially as the alkali metal, potassium, or sodium salts. Sodium or potassium toluene sulfonate is especially preferred. The hydrotrope is added at levels of from about 0% to about 10% by weight of the composition. Levels of from about 2% to 8% are preferred. The upper limit of about 10% is set by increasing dilution of the product by an ingredient substantially inert so far as sudsing and detergency are concerned. The lower limit is in the amount required to achieve a homogeneous solution. It will be appreciated that it is necessary that the formulations of this invention should be liquid at somewhat higher and at somewhat lower temperatures than usual room temperature. The amount of hydrotrope salt used is preferably the minimum amount which will hold the ingredients in solution at the temperature to which it is desired that the formula can be cooled without phase separation.

Solubilizing agents also can be added, if necessary, and those preferred are lower alcohols such as methyl, ethyl and propyl alcohols. They are generally employed at a level of from about 0% to about 25% by weight of the composition and preferably between about 5% to 15% by weight.

As hereinbefore mentioned, various minor ingredients can also be added to the compositions of the present invention. Such normal and desirable additives include perfumes, viscosity central agents, opacifiers, and pigments. In addition, inert materials such as water soluble inorganic salts can also be present in minor amounts, generally as impurities from the various ingredients or as opacifier stabilizers. For example, ethylene glycol distearate or polystyrene can be used as opacifiers in amounts of up to 3% by weight of the composition.

The following compositions are given in Table I by way of examples only and are not intended to limit the scope of the present invention.

Excellent performing light-duty compositions can be prepared having by weight ratios given in Table I in the active detergent ingredient. The compositions prepared accordingly, rapidly produce a synergistically high level of suds volume which is stable over a prolonged period. These compositions are especially useful for dishwashing and the laundering of fine and delicate fabrics as well as the washing of woolens, i.e. sweaters, carpets, etc., where copious amounts of stable suds are desirable. In Table I the Detergent A containing 12 carbon atoms, corresponds to the composition presented in FIGURE 2, graph line V, Detergent A containing 14 carbon atoms corresponds to FIGURE 2, graph line III, and Detergent A containing 16 carbon atoms corresponds to FIGURE 2, graph line IV. I

The following examples represent light-duty detergent compositions which can be prepared according to the present invention. Each provides the valuable synergistic results which are described above.

TABLE I Examples DETERGENT A Detergent A Containing 12 Carbon Atoms Detergent A Containing 14 Carbon Atoms Detergent A Containing 16 Carbon Atoms DETERGENT n Zwitterionio Quaternary Ammonium Compounds:

3-(N,N-dimethyl-N-docedyl-ammonio)- 2-hydr0xypropane-1'sul fonate 3- (N ,N-dimethyl-N-coconut-ammonio)- 2-hydroxypropanc-l-sulfonate 3- (N ,N-dimethyl-N-tetradecyl-amrnonio)- 2-hydroxypropane-1-sulionate 3-(N,N-dimethyl-N-cooonut-ammonio) propane-l-sulfonate Tertiary Amine Oxide:

Dodecyl dimethyl amine oxide Tetradecyl dimethyl amine oxide Coconut alkyl dimethyl amine oxide Coconut alkyl diethyl amine oxide. Tertiary Phosphine Oxide:

Dodecyl dimethyl phosphine oxide Tetradecyl dimethyl phosphine oxide Coconut alkyl dimethyl phosphine oxide Coconut alkyl diethyl phosphine oxide Weight Ratio of Detergent A to Detergent B in Detergent Composition 311 1:1 1:3 2:1 1:1 1:2 :1 1.5:1 1:4 4:1 5:1 1:5 2:1 1:2 1:1 1:1 3:1

Percent Total Detergent in Composition, Balance belllg Water 30 25 20 15 28 45 40 30 30 20 85 80 28 32 Example 18 17.5% Detergent A as used in FIGURE 2, graph line III 17.5% 3 (N,N di-methyl-N-dodecyl-ammonio)-2-hydroxypropane-l-sulfonate 10.0% Potassium pyrophosphate 1 8.0% Potassium toluene sulfonate 3.0% Ethyl alcohol 44.0% Water.

Example 19 20.0% Detergent A as used in FIGURE 2, graph line IV 10.0% Dodecyldimethyl amine oxide 8.0% Trisodium-ethane-l-hydroxy-l,l-diphosphonate 2.0% Ethyl alcohol 60.0% Water.

Example 20 8.0% Detergent A as used in FIGURE 2, graph line V 17.0% Dodecyldimethyl phosphine oxide 8.0% Tripotassium salt of nitrilotriacetate 67.0% Water.

Example 21 Example 22 25.0% Detergent A as used in FIGURE 2 graph line III 5.0% 'Dodecyldimethyl amine oxide 30.0% Tetrapotassium pyrophos-phate 40.0% Water.

Each of the preceding compositions can perform exceptionally well as light-duty liquid detergent compositions. They find special application as dishwashing detergent compositions. All percentages and ratios herein are by weight.

While emphasis has been placed in the foregoing description of the present invention upon detergent formulation in liquid form, the compositions herein can also be prepared in solid formulations such as granules, flakes,

powders and other solid particulate forms. Such solid formulations can also contain the synergistic combination of the herein-described detergent compounds in admixture with the builders also described herein ranging from lightly built compositions to heavily built detergent compositions. A typical example of a heavy duty or heavily built granular detergent composition can contain about 17.5% of an active detergent mixture described herein, about 50% sodium tripolyphosphate, about 24% sodium sulfate, and about 8.5% sodium silicate.

It has also been discovered that the synergistic sudsing properties of the novel ternary detergent composition described herein can be even further enhanced by adding to saidcomposition from about 0.1% to about 0.3% by weight of a water hardness salt such as magnesium sulfate, magnesium chloride,. calcium sulfate and calcium chloride, or mixtures thereof. Other well known water hardness salts can also be used such as iron salts and the like. Preferablyfrom about 0.15% to 0.25% by weight of the inorganic salt should be present in the product.

The suds building effect is more pronounced in relatively soft water but it is also effective in so-called medium hard Water or hard Water. A surprising aspect of this discovery is that the marked improvement in sudsing is not obtained if the equivalent amount of water hardness salts is added to the water solution instead of being present in the detergent product.

It should be understood that the foregoing detailed description and specific examples, while indicating general and preferred embodiments of the present invention, a

are given by way of illustration only. Since various changes and modifications within the spirit and scopeof the invention will become apparent to those skilled in the art from this detailed description.

We claim: I

1. A detergent composition consisting essentially of a synergistic mixture of Detergent A and Detergent B wherein Detergent A is a mixture of from about 30% to about 70% of Component A, from about 20% to about 70% of Component B and from about 2% to about 15% of Component C, wherein:

(a) said Component A is a mixture of double-bond positional isomers of water-soluble salts of a'lkene-lsulfonic acids containing from about 12 to about 16 carbon atoms, said mixture of positional isomers including about 10% to about 25% of an alpha-beta unsaturated isomer, about 30% to about 70% of a 19 beta-gamma unsaturated isomer, about to about 25 of a gamma-delta unsaturated isomer, and about 5% to about of a delta-epsilon unsaturated isomer;

(b) said Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 12 to about 16 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom at least 90% of the hydroxyl radical substitutions being in the 3, 4 and 5 positions;

(c) said Component C is a mixture comprising from 30-95% water-soluble salts of alkene disulfonate containing from about 12 to about 16 carbon atoms, and from about 5% to about 70% water-soluble salts of hydroxy disulfonates containing from about 12 to about 16 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the site of attachment of said second sulfonate group;

and wherein Detergent B is a compound selected from the group consisting of:

(1) zwitterionic quaternary ammonium compounds having the formula 3 R11IICH2]?,4SO3

wherein:

R is an alkyl radical containing from 12 to 14 carbon atoms,

(3) a tertiary phosphine oxide detergent compoundv having the formula R'R"R"'P O, wherein in both (2) and (3) R is an alkyl or monohydroxyalkyl radical containing from about 12 to 14 carbon atoms, R" and R' are each members selected from the group, consisting of methyl, ethyl and hydroxyethyl; the ratio of Detergent A to Detergent B being from about 5:1 to about 1:5 by weight.

2. A detergent composition prepared according to claim 1 wherein the ratio of Detergent A to Detergent B is from 3:1 to 1:3 by weight.

3. A detergent composition prepared according to claim 1 wherein Detergent B is 3-(N,N-dimethyl-N-dodecy1- ammonio)-2-hydroxypropane-l-sulfonate.

4. A detergent composition prepared according to claim 1 wherein Detergent B is 3-(N,N-dimethyl-N-coconutalkylammonio)-2-hydroxypropane-l-sulfonate.

5. A detergent composition prepared according to claim 1 wherein Detergent B is dodecyldimethyl amine oxide.

6. A detergent composition prepared according to claim 1 wherein Detergent B is tetradecyldimethyl amine oxide.

7. A detergent composition prepared according to claim 1 wherein Detergent B is dodecyldimethyl phosphine oxide.

8. A detergent composition prepared according to claim 1 wherein Detergent B is tetra-decyldimethyl phosphine oxide.

9. A liquid detergent composition consisting essentially of from about 5% to about 50% of the composition described in claim 1, and from about 50% to about 95% Water.

10. A liquid detergent composition of claim 9 wherein the detergent composition is present at from about 10% to about 35% by weight of the composition and the water is present at from about 65% to 11. A liquid detergent composition consisting essentially of from about 5% to about 50% of the detergent composition described in claim 1, water, and from about 4% to about 30% of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic alkaline sequestering builder salts and mixtures thereof.

12. A liquid detergent composition of claim 11 wherein the detergency builder is employed at a level of from about 8% to about 25%.

13. A liquid detergent composition of claim 11 Wherein the detergency builder is potassium pyrophosphate.

14. A liquid detergent composition of claim 11 wherein the detergency builder is trisodium ethane-l-hydroxy- 1,1-diphosphonate.

15. A liquid detergent composition consisting essentially of from about 5% to about 50% of the detergent composition described in claim 1; and from about 4% to about 30% of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic alkaline sequestering builder salts and mixtures thereof; from about 0% to about 10% of a hydrotrope selected from the group consisting of the water-soluble sodium, potassium, ethanolammonium, diethanolammonium, and triethanolammonium salts of benzene sulfonate, xylene sulfonate and toluene sulfonate; from about 0% to about 25% of a solubilizing agent selected from the group consisting of methyl, ethyl and propyl alcohols; with the balance being water.

16. A liquid detergent composition having synergistic sudsing properties consisting essentially of from about 10% to about 35% of the detergent composition described in claim 1; and from about 8% to about 25% of a detergency builder selected from the group consisting of water soluble inorganic alkaline builder salts, organic alkaline sequestering builder salts and mixtures thereof; from about 2% to about 8% of a hydrotrope selected from the group consisting of the water-soluble sodium, potassium, ethanolammonium, diethanolammonium, and triethanolammoniurn salts of benzene sulfonate, xylene sulfonate and toluene sulfonate; from about 5% to about 15% of a solubilizing agent selected from the group consisting of methyl, ethyl and propyl alcohols, with the balance being water.

17. A detergent composition according to claim 1 which also contains from about 0.1% to about 0.3% by weight of a water hardness salt selected from the group consisting of magnesium sulfate, magnesium chloride, calcium sulfate and calcium chloride.

18. A detergent composition according to claim 17 wherein the water hardness salt is present at a percentage of from about 0.15% to about 0.25% by weight.

References Cited UNITED STATES PATENTS 2,061,617 11/1936 Downing et al. 2,061,618 11/1936 Downing et al. 2,061,620 11/1936 Downing et al. 2,477,383 7/1949' Lewis. 3,072,618 1/ 1963 Turbak.

(Other references on following page) 21 FOREIGN PATENTS 651,783 8/1964 Belgium.

OTHER REFERENCES Alpha-Olefins in the Surfactant Industry, J. Amer. Oil Chem. Society, T. H. Liddicoat, November 1963, 631- 636.

Alkene Sulfonates Made by New Method, Chemical and Engineering News, A. P. Turbak, (Apr. 15, 1963), pp. 96-98.

The Reactions of Sulfur Trioxide and of Its Adducts with Organic Compounds, Chemical Review 62, #6, December 1962, pp. 549-589.

22 fonic Acids, I. Z-Hydroxy-l-n-Alkanesulfonic Acids, F. Puschel and Claus Kaiser, 2903-13, October 1964.

Chem. Ber. 97 #10, 2917-25 (October 1964) Higher Molecular Aliphatic Sulfonic Acids, II 3-Hydroxy-1-n- Alkanesulfonic Acids and their Inner Esters (1,3-Sultones), F. Puschel and Claus Kaiser.

Chem. Ber., 97 #10, 2926-33 (October 1964) Higher Molecular Unsaturated Sulfonic Acids and the Hydrolysis of 1,3-Alkanesultones, F. Puschel and Claus Kaiser.

Chem. Ber., 98 735-742 (1965) Higher Molecular AliphaticSulfonic Acids, IV Sulfonation of Un-branched Alpha-Olefins with S0 F. Puschel and Claus Kaiser.

LEON D. RO'SDOL, Primary Examiner.

Chem. Berg. 97, #10, Higher Molecular Aliphatic Sul- 15 S. E. DARDEN, Assistant Examiner. 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A SYNERGISTIC MIXTURE OF DETERGENT A AND DETERGENT B WHEREIN DETERGENT A IS A MIXTURE OF FROM ABOUT 30% TO ABOUT 70% OF COMPONENT A, FROM ABOUT 20% TO ABOUT 70% OF COMPONENT B AND FROM ABOUT 20% TO ABOUT 15% OF COMPONENT C, WHEREIN: (A) SID COMPONENT A IS A MIXTURE OF DOUBLE-BOND POSITIONAL ISOMERS OF WATER-SOLUBLE SALTS OF ALKENE-1SULFONIC ACIDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID MIXTURE OF POSITIONAL ISOMERS INCLUDING ABOUT 10% TO ABOUT 25% OF AN ALPHA-BETA UNSATURATED ISOMER, ABOUT 30% TO ABOUT 70% OF A BETA-GAMMA UNSATURATED ISOMER, ABOUT 5% TO ABOUT 25% OF A GAMMA-DELTA UNSATURATED ISOMER, AND ABOUT 5% TO ABOUT 10% OF A DELTA-EPSILON UNSATURATED ISOMER; (B) SAID COMPONENT B IS A MIXTURE OF WATER-SOLUBLE SALTS OF BIFUNCTIONALLY-SUBSTITUTED SULFUR-CONTAINING SATURATED ALIPHATIC COMPOUNDS CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, THE FUNCTIONAL UNITS BEING HYDROXY AND SULFONATE RADICALS WITH THE SULFONATE RADICAL ALWAYS BEING ON THE TERMINAL CARBON AND THE HYDROXYL RADICAL BEING ATTACHED TO A CARBON ATOM AT LEAST TWO CARBON ATOMS REMOVED FROM THE TERMINAL CARBON ATOM AT LEAST 90% OF THE HYDROXYL RADICAL SUBSTITUTION BEING IN THE 3, 4 AND 5 POSITIONS; (C) SAID COMPONENT C IS A MIXTURE CONTAINING FROM 30-95% WATER-SOLUBLE SALTS OF ALKENE DISFULFONATE CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, AND FROM ABOUT 5% TO ABOUT 70% WATER-SOLUBLE SALTS OF HYDROXY DISULFONATES CONTAINING FROM ABOUT 12 TO ABOUT 16 CARBON ATOMS, SAID ALKENE DISULFONATES CONTAINING A SULFONATE GROUP ATTACHED TO A TERMINAL CARBON ATOM AND A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOMS NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, THE ALKENE DOUBLE BOND BEING DISTRIBUTED BETWEEN THE TERMINAL CARBON ATOM AND ABOUT THE SEVENTH CARBON ATOM, SAID HYDROXY DISULFONATES BEING SATURATED ALIPHATIC COMPOUNDS HAVING A SULFONATE RADICAL ATTACHED TO A TERMINAL CARBON, A SECOND SULFONATE GROUP ATTACHED TO AN INTERNAL CARBON ATOM NOT MORE THAN ABOUT SIX CARBON ATOMS REMOVED FROM SAID TERMINAL CARBON ATOM, AND A HYDROXY GROUP ATTACHED TO A CARBON ATOM WHICH IS NOT MORE THAN ABOUT FOUR CARBON ATOMS REMOVED FROM THE SITE OF ATTACHMENT OF SAID SECOND SULFONATE GROUP; AND WHEREIN DETERGENT B IS A COMPOUND SELECTED FROM THE GROUP CONSISTING OF: (1) ZWITTERIONIC QUATERNARY AMMONIUM COMPOUNDS HAVING THE FORMULA 